Fungicidal Mixtures Comprising Substituted 1-methylpyrazol-4-ylcarboxanilides

ABSTRACT

Fungicidal mixtures, comprising as active components
     1) at least one 1-methylpyrazol-4-ylcarboxanilide of the formula I   

     
       
         
         
             
             
         
       
         
         
           
             where R 1 ═C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, R 2 =hydrogen or halogen, X=hydrogen or halogen, Q=direct bond, a cyclopropylene or an anellated bicyclo[2.2.1]heptane ring; R 3 ═C 1 -C 6 -alkyl, cyclopropyl or phenyl substituted with two or three halogen atoms or a trifluoromethylthio radical;
 
and
 
           
         
         2) at least one active compound II, selected from the active compound groups A) to K):
       A) organo(thio)phosphates;   B) carbamates;   C) pyrethroids;   D) growth regulators;   E) GABA antagonist compounds;   F) macrocyclic lactone insecticides;   G) METI I acaricides;   H) METI II and III compounds;   J) oxidative phosphorylation inhibitor compounds;   K) various compounds;
 
in a synergistically effective amount, methods for controlling harmful fungi using mixtures of at least one compound I and at least one active compound II, the use of a compound I or compounds I with active compounds II for preparing such mixtures, and also compositions and seed comprising such mixtures.

The present invention relates to mixtures for controllingphytopathogenic harmful fungi comprising, as active components,

-   1) at least one 1-methylpyrazol-4-ylcarboxanilides of the formula I

-   -   in which the substituents are as defined below:    -   R¹ is C₁-C₄-alkyl or C₁-C₄-haloalkyl;    -   R² is hydrogen or halogen;    -   X is hydrogen or fluorine;    -   Q is a direct bond, a cyclopropylene or an anellated        bicyclo[2.2.1]heptane ring;    -   R³ is C₁-C₆-alkyl, cyclopropyl or phenyl substituted with two or        three halogen atoms or with a trifluoromethylthio radical;

and

-   2) at least one active compound II, selected from the active    compound groups A) to

K):

-   -   A) organo(thio)phosphates selected from the group consisting of        acephate, azamethiphos, azinphos-methyl, chlorpyrifos,        chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos,        dicrotophos, dimethoate, disulfoton, ethion, fenitrothion,        fenthion, isoxathion, malathion, methamidophos, methidathion,        methyl-parathion, mevinphos, monocrotophos, oxy-demeton-methyl,        paraoxon, parathion, phenthoate, phosalone, phosmet,        phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos,        prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos        and trichlorfon;    -   B) carbamates selected from the group consisting of: alanycarb,        aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran,        carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl,        oxamyl, pirimicarb, propoxur, thiodicarb and triazamate;    -   C) pyrethroids selected from the group consisting of allethrin,        bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin,        alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin,        deltamethrin, esfenvalerate, etofenprox, fenpropathrin,        fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin,        prallethrin, pyrethrin I and II, resmethrin, silafluofen,        tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin,        transfluthrin, profluthrin and dimefluthrin;    -   D) growth regulators selected from the group consisting of the        following        -   a) chitin synthesis inhibitors: benzoylureas:            chlorfluazuron, cyramazin, -flucycloxuron, hexaflumuron,            lufenuron, novaluron, triflumuron; buprofezin, diofenolan,            hexythiazox, etoxazole and clofentazine;        -   b) ecdysone antagonists: halofenozide, methoxyfenozide,            tebufenozide, and azadirachtin;        -   c) juvenoids: pyriproxyfen, methoprene and fenoxycarb;        -   d) lipid biosynthesis inhibitors: spirodiclofen,            spiromesifen and spirotetramat;    -   E) GABA antagonist compounds selected from the group consisting        of endosulfan, ethiprole, vaniliprole, pyrafluprole, pyriprole        and the phenylpyrazole of the formula E¹

-   -   F) macrocyclic lactone insecticides selected from the group        consisting of abamectin, emamectin, milbemectin, lepimectin,        spinosad and spinetoram;    -   G) METI I acaricides selected from the group consisting of        fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad and flufenerim;    -   H) METI II and III compounds selected from the group consisting        of acequinocyl, fluacyprim and hydramethylnon;    -   J) oxidative phosphorylation inhibitor compounds selected from        the group consisting of cyhexatin, diafenthiuron, fenbutatin        oxide and propargite;    -   K) various compounds selected from the group consisting of        amidoflumet, benclothiaz, bifenazate, bistrifluron, cartap,        chlorfenapyr, cryomazine, cyazypyr (HGW86), cyenopyrafen,        cyflumetofen, flonicamid, flubendiamide, flupyrazofos,        imicyafos, indoxacarb, metaflumizone, piperonyl butoxide,        pymetrozine, pyridalyl, pyrifluquinazon, thiocyclam and the        thiazole compound of formula K¹

in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmfulfungi using a mixture of at least one compound I and at least one of theactive compounds II, to the use of the compound(s) I with activecompound(s) II for preparing such mixtures, and also to compositions andseed comprising such mixtures.

The 1-methylpyrazol-4-ylcarboxanilides of the formula I, referred toabove as component 1), their preparation and their action againstharmful fungi are known from the literature (cf., for example, EP-A 545099, EP-A 589 301, WO 99/09013, WO 03/010149, WO 2003/70705, WO03/074491 and WO 04/035589), or they can be prepared in the mannerdescribed therein.

However, the known 1-methylpyrazol-4-ylcarboxanilides of the formula Iare, in particular at low application rates and with regard to theirsprectrum of activity, not entirely satisfactory.

The active compounds II mentioned above as component 2), theirpreparation and their action against harmful fungi are generally known(cf., for example, http://www.hclrss.demon.co.uk/index.html); they arecommercially available.

It is an object of the present invention, with a view to reducing theapplication rates and broadening the activity spectrum of the compoundsI, to provide mixtures which, at a reduced total amount of activecompounds applied, have improved activity against harmful fungi, inparticular for specific indications.

We have accordingly found that this object is achieved by the mixtures,defined at the outset, of the active compounds I and II. Moreover, wehave found that simultaneous, that is joint or separate, application ofat least one compound I and at least one of the active compounds II orsuccessive application of the compound(s) I and at least one of theactive compounds II allows better control of harmful fungi than ispossible with the individual compounds alone (synergistic mixtures).

By simultaneous, that is joint or separate, application of compound(s) Iwith at least one active compound II, the fungicidal activity isincreased in a superadditive manner.

The compounds I can be present in different crystal modifications, whichmay differ in biological activity.

In the formula I, halogen is fluorine, chlorine, bromine or iodine,preferably fluorine or chlorine;

C₁-C₄-alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl,1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, preferably methylor ethyl;

C₁-C₆-alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl,1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, n-hexyl or1,3-dimethylbutyl, in particular 1-methylethyl or 1,3-dimethylbutyl;

C₁-C₄-haloalkyl is a partially or fully halogenated C₁-C₄-alkyl radical,where the halogen atom(s) is/are in particular fluorine, chlorine and/orbromine, i.e., for example, chloromethyl, bromomethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl,2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichioroethyl, pentafluoroethyi, heptafluoropropyl ornonafluorobutyl, in particular halomethyl, with particular preferenceCH₂—Cl, CH(Cl)₂, CH₂—F, CHF₂, CF₃, CHFCl, CF₂Cl or CF(Cl)₂, inparticular CHF₂ or CF₃;

C₁-C₄alkylthio is SCH₃, SC₂H₅, SCH₂—C₂H₅, SCH(CH₃)₂, n-butylthio,SCH(CH₃)—C₂H₅, SCH₂—CH(CH₃)₂ or SC(CH₃)₃, preferably SCH₃ or SC₂H₅.

Preferred 1-methylpyrazol-4-ylcarboxanilides I are, on the one hand,those in which X is hydrogen.

On the other hand, preferred compounds I are those in which X isfluorine.

For the mixtures according to the invention, preference is given tocompounds of the formula I in which R¹ is methyl or halomethyl, inparticular CH₃, CHF₂, CH₂F, CF₃, CHFCl or CF₂Cl, particularly preferablyCH₃ or CHF₂.

Preference is furthermore given to compounds I in which R² is hydrogen,fluorine or chlorine, in particular hydrogen or fluorine.

Preference is furthermore given to those compounds I in which R³ isphenyl substituted by two or three halogen atoms, in particular3,4-dichlorophenyl or 3,4,5-trifluorophenyl.

Moreover, preference is given toN-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide,N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5-fluor-1H-pyrazole-4-carboxamide(common name: Penflufen),N-(2-Bicycloprop-2-ylphenyl)-3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide(common name: Sedaxane),N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide(common name: Sedaxane; trans diastereoisomer), isopyrazam and bixafen.

Very particularly preferred areN-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamideand bixafen, most preferred isN-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro-methyl-1-methyl-1H-pyrazole-4-carboxamide(compound Ia).

With respect to the active compounds II, preference is given to mixturesof a 1-methylpyrazol-4-ylcarboxanilide I with at least one activecompound II selected from the group of the A) organo(thio)phosphates, inparticular acephate, chlorpyrifos, diazinon, dichlorvos, dimethoate,fenitrothion, methamidophos, methidathion, methyl-parathion,monocrotophos, phorate, profenofos or terbufos.

Very particularly preferred compounds II selected from A) are acephate,chlorpyrifos, dimethoate, methamidophos and terbufos.

Preference is also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the B) carbamates, in particular aldicarb,carbaryl, carbofuran, carbosulfan, methomyl or thiodicarb.

Very particularly preferred compounds II selected from B) are aldicarband carbofuran.

Preference is given to mixtures of a 1-methylpyrazol-4-ylcarboxanilide Iwith at least one active compound selected from the group of the C)pyrethroids, in particular bifenthrin, cyfluthrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate,lambda-cyhalothrin, permethrin or tefluthrin.

Very particularly preferred compounds II selected from C) arebifenthrin, cypermethrin, alpha-cypermethrin, deltamethrin,lambda-cyhalothrin and tefluthrin.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the D) growth regulators, in particularlufenuron or spirotetramat, very particularly preferred spirotetramat.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the E) GABA antagonist compounds, inparticular endosulfan.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the F) macrocyclic lactone insecticides, inparticular abamectin, emamectin, spinosad or spinetoram.

Very particularly preferred compounds II selected from F) are abamectin,spinosad and spinetoram.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the G) METI I acaricides.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the H) METI II and III compounds, inparticular hydramethylnon.

Preference is furthermore also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the J) oxidative phosphorylation inhibitorcompounds, in particular fenbutatin oxide.

Preference is also given to mixtures of a1-methylpyrazol-4-ylcarboxanilide I with at least one active compoundselected from the group of the K) various compounds, in particularchlorfenapyr, cyazypyr (HGW86), cyflumetofen, flonicamid, flubendiamide,indoxacarb and metaflumizone.

Very particularly preferred compounds II selected from K) arechlorfenapyr, cyazypyr (HGW86), cyflumetofen, flubendiamide andindoxacarb.

Preference is also given to three-component mixtures of one1-methylpyrazol-4-ylcarboxanilide I with two of the active compounds IImentioned above.

Preference is also given to three-component mixtures of one compound ofthe formula I with two of the active compounds II mentioned above orwith one active compound II and a further fungicidally active compoundIII selected from active compound groups L) to S):

L) strobilurins

-   -   azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin,        kresoxim-methyl, meto-minostrobin, orysastrobin, picoxystrobin,        pyraclostrobin, pyribencarb, triflox-ystrobin,        2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)-2-methoxyimino-N-methyl-acetamide,        3-methoxy-2-(2-(N-(4-methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic        acid methyl ester, methyl        (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate        and        2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide;        M) carboxamides    -   carboxanilides: benalaxyl, benalaxyl-M, benodanil, boscalid,        carboxin, fenfuram, fenhexamid, flutolanil, furametpyr,        isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl,        metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin,        penthiopyrad, tecloftalam, thifluzamide, tiadinil;    -   carboxylic morpholides: dimethomorph, flumorph;    -   benzoic acid amides: flumetover, fluopicolde, fluopyram,        zoxamide,        N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide;    -   other carboxamides: carpropamid, dicyclomet, mandiproamid,        oxytetracyclin, silthiofarm and        N-(6-methoxy-pyridin-3-yl)cyclopropanecarboxylic acid amide;        N) azoles    -   triazoles: azaconazole, bitertanol, bromuconazole,        cyproconazole, difenoconazole, diniconazole, diniconazole-M,        epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,        flutriafol, hexaconazole, imibenconazole, ipconazole,        metconazole, myclobutanil, oxpoconazole, paclobutrazole,        penconazole, propiconazole, prothioconazole, simeconazole,        tebuconazole, tetraconazole, triadimefon, triadimenol,        triticonazole, uniconazole,        1-(4-chloro-phenyl)-2-([1,2,4]triazol-1-yl)-cycloheptanol;    -   imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz,        triflumizol;    -   benzimidazoles: benomyl, carbendazim, fuberidazole,        thiabendazole;    -   others: ethaboxam, etridiazole, hymexazole and        2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;        P) heterocyclic compounds    -   pyridines: fluazinam, pyrifenox,        3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,        3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,        2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine,        3,4,5-trichloro-pyridine-2,6-di-carbonitrile,        N-(1-(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloronicotinamide,        N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloronicotinamide;    -   pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol,        ferimzone, mepanipyrim, nitrapyrin, nuarimol, pyrimethanil;    -   piperazines: triforine;    -   pyrroles: fenpiclonil, fludioxonil;    -   morpholines: aldimorph, dodemorph, dodemorph-acetate,        fenpropimorph, tridemorph;    -   piperidines: fenpropidin;    -   dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;    -   non-aromatic 5-membered heterocycles: famoxadone, fenamidone,        octhili-none, probenazole,        5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1-carbothioic        acid S-allyl ester;    -   others: acibenzolar-S-methyl, amisulbrom, anilazin,        blasticidin-S, captafol, captan, chinomethionat, dazomet,        debacarb, diclomezine, difenzoquat, difen-zoquat-methylsulfate,        fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid,        pyroquilon, quinoxyfen, triazoxide, tricyclazole,        2-butoxy-6-iodo-3-propylchromen-4-one,        5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole,        5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,        6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-ethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-octyl-5-propyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        5-methoxymethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine,        6-octyl-5-trifluoromethyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine        and        5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine;        Q) carbamates    -   thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam,        methasulpho-carb, metiram, propineb, thiram, zineb, ziram;    -   carbamates: benthiavalicarb, diethofencarb, flubenthiavalicarb,        iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal        and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic        acid-(4-fluorophenyl) ester;        R) other fungicidal active substances    -   guanidines: guanidine, dodine, dodine free base, guazatine,        guazatine-acetate, iminoctadine, iminoctadine-triacetate,        iminoctadine-tris(albesilate);    -   antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate,        streptomycin, polyoxine, validamycin A;    -   nitrophenyl derivates: binapacryl, dinobuton, dinocap,        nitrthal-isopropyl, tecnazen,    -   organometal compounds: fentin salts, such as fentin-acetate,        fentin chloride or fentin hydroxide;    -   sulfur-containing heterocyclyl compounds: dithianon,        isoprothiolane;    -   organophosphorus compounds: edifenphos, fosetyl,        fosetyl-aluminum, ipro-benfos, phosphorous acid and its salts,        pyrazophos, tolclofos-methyl;    -   organochlorine compounds: chlorothalonil, dichlofluanid,        dichlorophen, flusul-famide, hexachlorobenzene, pencycuron,        pentachlorphenole and its salts, phthalide, quintozene,        thiophanate-methyl, tolylfluanid,        N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;    -   inorganic active substances: Bordeaux mixture, copper acetate,        copper hydroxide, copper oxychloride, basic copper sulfate,        sulfur;    -   others: biphenyl, bronopol, cyflufenamid, cymoxanil,        diphenylamin, metrafenone, mildiomycin, oxin-copper,        prohexadione-calcium, spiroxamine, tolylfluanid,        N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl        acetamide,        N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine,        N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine and        N′-(5-difluoromethyl-2-methyl-4-(3-tri-methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine.        S) growth regulators    -   abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,        brassinolide, butralin, chlormequat (chlormequat chloride),        choline chloride, cyclanilide, daminozide, dikegulac,        dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin,        flurprimidol, flu-thiacet, forchlorfenuron, gibberellic acid,        inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide,        mepiquat (mepiquat chloride), naphthaleneacetic acid,        N-6-benzyladenine, paclobutrazol, prohexadione        (prohexadione-calcium), prohy-drojasmon, thidiazuron,        triapenthenol, tributyl phosphorotrithioate,        2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;

The active compounds III mentioned above, their preparation and theiraction against harmful fungi are generally known (cf., for example,http://www.hclrss.demon.co.uk/index.html); they are commerciallyavailable. The compounds described by IUPAC nomenclature, theirpreparation and their fungicidal activity are also known (cf. Can. J.Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE19650197; DE 10021412; DE 102005009458; U.S. Pat. No. 3,296,272; U.S.Pat. No. 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783;WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO06/87343; WO 07/82098; WO 07/90624).

Preference is also given to three-component mixtures comprising acompound I (component 1) and at least one active substance II selectedfrom the strobilurines of group L) (component 2) and particularlyselected from azoxystrobin, dimoxystrobin, fluoxastrobin,kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin andtriflox-ystrobin.

Preference is also given to three-component mixtures comprising acompound I (component 1) and at least one active substance II selectedfrom the carboxamides of group M) (component 2) and particularlyselected from fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph,flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid andmandipropamid.

Preference is given to three-component mixtures comprising a compound offormula I (component 1) and at least one active substance II selectedfrom the azoles of group N) (component 2) and particularly selected fromcyproconazole, difenoconazole, epoxiconazole, fluquinconazole,flusilazole, flutriafol, metconazole, myclobutanil, penconazole,propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole,tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl,carbendazim and ethaboxam.

Preference is also given to three-component mixtures comprising acompound I (component 1) and at least one active substance II selectedfrom the heterocyclic compounds of group P) (component 2) andparticularly selected from fluazinam, cyprodinil, fenarimol,mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph,fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin,famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl,captafol, folpet, fenoxanil and quinoxyfen.

Preference is also given to three-component mixtures comprising acompound I (component 1) and at least one active substance II selectedfrom the carbamates of group Q) (component 2) and particularly selectedfrom mancozeb, metiram, propineb, thiram, iprovalicarb,flubenthiavalicarb and propamocarb.

Preference is also given to three-component mixtures comprising acompound I (component 1) and at least one active substance II selectedfrom the fungicides given in group R) (component 2) and particularlyselected from dithianon, fentin salts, such as fentin acetate, fosetyl,fosetyl-aluminium, H₃PO₃ and salts thereof, chlorthalonil,dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide,copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone,spiroxamine and5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]-triazolo[1,5-a]pyrimidine.

Preference is also given to four-component mixtures of compounds I andII with two futher active compounds selected from compounds II and IIImentioned above.

Preferred active compound combinations are listed in tables 1 to 9below:

TABLE 1 Active compound combinations of compounds I with activecompounds II of group A): Compound Compound Mixture I II No. A.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- acephatemethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- acephatefluor-1H-pyrazole-4-carboxamide No. A.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- acephatemethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.4 isopyrazam acephateNo. A.5 bixafen acephate No. A.6N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- chlorpyrifosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.7N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- chlorpyrifosfluor-1H-pyrazole-4-carboxamide No. A.8N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- chlorpyrifosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.9 isopyrazamchlorpyrifos No. A.10 bixafen chlorpyrifos No. A.11N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- dimethoate,methyl-1-methyl-1H-pyrazole-4-carboxamide No. A.12N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- dimethoate,fluor-1H-pyrazole-4-carboxamide No. A.13N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- dimethoate,methyl-1-methyl-1H-pyrazole-4-carboxamide No. A.14 isopyrazamdimethoate, No. A.15 bixafen dimethoate, No. A.16N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- methamidophosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.17N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- methamidophosfluor-1H-pyrazole-4-carboxamide No. A.18N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- methamidophosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.19 isopyrazammethamidophos No. A.20 bixafen methamidophos No. A.21N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- terbufosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.22N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- terbufosfluor-1H-pyrazole-4-carboxamide No. A.23N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- terbufosmethyl-1-methyl-1H-pyrazole-4-carboxamide No. A.24 isopyrazam terbufosNo. A.25 bixafen terbufos

TABLE 2 Active compound combinations of compounds I with activecompounds II of group B): Compound Compound Mixture I II No. B.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- aldicarbmethyl-1-methyl-1H-pyrazole-4-carboxamide No. B.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- aldicarbfluor-1H-pyrazole-4-carboxamide No. B.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- aldicarbmethyl-1-methyl-1H-pyrazole-4-carboxamide No. B.4 isopyrazam aldicarbNo. B.5 bixafen aldicarb No. B.6N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- carbofuranmethyl-1-methyl-1H-pyrazole-4-carboxamide No. B.7N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- carbofuranfluor-1H-pyrazole-4-carboxamide No. B.8N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- carbofuranmethyl-1-methyl-1H-pyrazole-4-carboxamide No. B.9 isopyrazam carbofuranNo. B.10 bixafen carbofuran

TABLE 3 Active compound combinations of compounds I with activecompounds II of group C): Compound Compound Mixture I II No. C.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- bifenthrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- bifenthrinfluor-1H-pyrazole-4-carboxamide No. C.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- bifenthrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.4 isopyrazam bifenthrinNo. C.5 bixafen bifenthrin No. C.6N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- cypermethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.7N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- cypermethrinfluor-1H-pyrazole-4-carboxamide No. C.8N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- cypermethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.9 isopyrazamcypermethrin No. C.10 bixafen cypermethrin No. C.11N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- alpha-cypermethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.12N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- alpha-cypermethrinfluor-1H-pyrazole-4-carboxamide No. C.13N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- alpha-cypermethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.14 isopyrazamalpha-cypermethrin No. C.15 bixafen alpha-cypermethrin No. C.16N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- deltamethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.17N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- deltamethrinfluor-1H-pyrazole-4-carboxamide No. C.18N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- deltamethrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.19 isopyrazamdeltamethrin No. C.20 bixafen deltamethrin No. C.21N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- lambda-cyhalothrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.22N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- lambda-cyhalothrinfluor-1H-pyrazole-4-carboxamide No. C.23N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- lambda-cyhalothrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.24 isopyrazamlambda-cyhalothrin No. C.25 bixafen lambda-cyhalothrin No. C.26N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- tefluthrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.27N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- tefluthrinfluor-1H-pyrazole-4-carboxamide No. C.28N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- tefluthrinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. C.29 isopyrazam tefluthrinNo. C.30 bixafen tefluthrin

TABLE 4 Active compound combinations of compounds I with activecompounds II of group D): Compound Compound Mixture I II No. D.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- spirotetramatmethyl-1-methyl-1H-pyrazole-4-carboxamide No. D.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- spirotetramatfluor-1H-pyrazole-4-carboxamide No. D.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- spirotetramatmethyl-1-methyl-1H-pyrazole-4-carboxamide No. D.4 isopyrazamspirotetramat No. D.5 bixafen spirotetramat

TABLE 5 Active compound combinations of compounds I with activecompounds II of group E): Compound Compound Mixture I II No. E.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- endosulfanmethyl-1-methyl-1H-pyrazole-4-carboxamide No. E.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- endosulfanfluor-1H-pyrazole-4-carboxamide No. E.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- endosulfanmethyl-1-methyl-1H-pyrazole-4-carboxamide No. E.4 isopyrazam endosulfanNo. E.5 bixafen endosulfan

TABLE 6 Active compound combinations of compounds I with activecompounds II of group F): Compound Compound Mixture I II No. F.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- abamectin, andmethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- abamectinfluor-1H-pyrazole-4-carboxamide No. F.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- abamectinmethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.4 isopyrazam abamectinNo. F.5 bixafen abamectin No. F.6N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- spinosadmethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.7N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- spinosadfluor-1H-pyrazole-4-carboxamide No. F.8N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- spinosadmethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.9 isopyrazam spinosadNo. F.10 bixafen spinosad No. F.11N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- spinetorammethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.12N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- spinetoramfluor-1H-pyrazole-4-carboxamide No. F.13N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- spinetorammethyl-1-methyl-1H-pyrazole-4-carboxamide No. F.14 isopyrazam spinetoramNo. F.15 bixafen spinetoram

TABLE 7 Active compound combinations of compounds I with activecompounds II of group H): Compound Compound Mixture I II No. H.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- hydramethylnonmethyl-1-methyl-1H-pyrazole-4-carboxamide No. H.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- hydramethylnonfluor-1H-pyrazole-4-carboxamide No. H.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- hydramethylnonmethyl-1-methyl-1H-pyrazole-4-carboxamide No. H.4 isopyrazamhydramethylnon No. H.5 bixafen hydramethylnon

TABLE 8 Active compound combinations of compounds I with activecompounds II of group J): Compound Compound Mixture I II No. J.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- fenbutatin oxidemethyl-1-methyl-1H-pyrazole-4-carboxamide No. J.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- fenbutatin oxidefluor-1H-pyrazole-4-carboxamide No. J.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- fenbutatin oxidemethyl-1-methyl-1H-pyrazole-4-carboxamide No. J.4 isopyrazam fenbutatinoxide No. J.5 bixafen fenbutatin oxide

TABLE 9 Active compound combinations of compounds I with activecompounds II of group K): Compound Compound Mixture I II No. K.1N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- chlorfenapyrmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.2N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- chlorfenapyrfluor-1H-pyrazole-4-carboxamide No. K.3N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- chlorfenapyrmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.4 isopyrazamchlorfenapyr No. K.5 bixafen chlorfenapyr No. K.6N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- cyazypyr (HGW86)methyl-1-methyl-1H-pyrazole-4-carboxamide No. K.7N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- cyazypyr (HGW86)fluor-1H-pyrazole-4-carboxamide No. K.8N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- cyazypyr (HGW86)methyl-1-methyl-1H-pyrazole-4-carboxamide No. K.9 isopyrazam cyazypyr(HGW86) No. K.10 bixafen cyazypyr (HGW86) No. K.11N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- cyflumetofenmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.12N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- cyflumetofenfluor-1H-pyrazole-4-carboxamide No. K.13N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- cyflumetofenmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.14 isopyrazamcyflumetofen No. K.15 bixafen cyflumetofen No. K.16N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- flubendiamidemethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.17N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- flubendiamidefluor-1H-pyrazole-4-carboxamide No. K.18N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- flubendiamidemethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.19 isopyrazamflubendiamide No. K.20 bixafen flubendiamide No. K.21N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- indoxacarbmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.22N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- indoxacarbfluor-1H-pyrazole-4-carboxamide No. K.23N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- indoxacarbmethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.24 isopyrazam indoxacarbNo. K.25 bixafen indoxacarb No. K.26N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoro- metaflumizonemethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.27N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5- metaflumizonefluor-1H-pyrazole-4-carboxamide No. K.28N-(trans-2-bicycloprop-2-ylphenyl)-3-difluoro- metaflumizonemethyl-1-methyl-1H-pyrazole-4-carboxamide No. K.29 isopyrazammetaflumizone No. K.30 bixafen metaflumizone

The mixtures of active substances can be prepared as compositionscomprising besides the active compounds at least one inert ingredient byusual means, e. g. by the means given for the compositions of compoundsI.

The mixtures of active substances according to the present invention aresuitable as fungicides, as are the compounds of formula I. They aredistinguished by an outstanding effectiveness against a broad spectrumof phytopathogenic fungi, especially from the classes of theAscomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn.Oomycetes). In addition, it is referred to the explanations regardingthe fungicidal activity of the compounds and the compositions containingcompounds I, respectively.

The mixtures of the compound(s) I with at least one of the activecompounds II, or the simultaneous, that is joint or separate, use of acompound I with at least one of the active compounds II, are/isdistinguished by an outstanding effectiveness against a broad spectrumof phytopathogenic fungi, including soil-borne fungi, which deriveespecially from the classes of the Plasmodiophoromycetes,Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).Some are systemically effective and they can be used in crop protectionas foliar fungicides, fungicides for seed dressing and soil fungicides.Moreover, they are suitable for controlling harmful fungi, which interalia occur in wood or roots of plants

The compounds I and the compositions according to the invention areparticularly important in the control of a multitude of phytopathogenicfungi on various cultivated plants, such as cereals, e. g. wheat, rye,barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet;fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries,blackberries or gooseberries; leguminous plants, such as lentils, peas,alfalfa or soybeans; oil plants, such as rape, mustard, olives,sunflowers, coconut, cocoa beans, castor oil plants, oil palms, groundnuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiberplants, such as cotton, flax, hemp or jute; citrus fruit, such asoranges, lemons, grape-fruits or mandarins; vegetables, such as spinach,lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes,cucurbits or paprika; lauraceous plants, such as avo-cados, cinnamon orcamphor; energy and raw material plants, such as corn, soybean, rape,sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines(table grapes and grape juice grape vines); hop; turf; natural rubberplants or ornamental and forestry plants, such as flowers, shrubs,broad-leaved trees or evergreens, e. g. conifers; and on the plantpropagation material, such as seeds, and the crop material of theseplants.

Preferably, compounds I and compositions thereof, respectively are usedfor controlling a multitude of fungi on field crops, such as potatoessugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton,soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits;vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans orsquashes.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e. g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants,including seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil. These young plants may also beprotected before transplantation by a total or partial treatment byimmersion or pouring.

Preferably, treatment of plant propagation materials with compounds Iand compositions thereof, respectively, is used for controlling amultitude of fungi on cereals, such as wheat, rye, barley and oats;rice, corn, cotton and soybeans.

The term “cultivated plants” is to be understood as including plantswhich have been modified by breeding, mutagenesis or genetic engineeringincluding but not limiting to agricultural biotech products on themarket or in development (cf.http://www.bio.org/speeches/pubs/er/agri_products.asp). Geneticallymodified plants are plants, which genetic material has been so modifiedby the use of recombinant DNA techniques that under naturalcircumstances cannot readily be obtained by cross breeding, mutations ornatural recombination. Typically, one or more genes have been integratedinto the genetic material of a genetically modified plant in order toimprove certain properties of the plant. Such genetic modifications alsoinclude but are not limited to targeted post-transtional modification ofprotein(s), oligo- or polypeptides e. g. by glycosylation or polymeradditions such as prenylated, acetylated or farnesylated moieties or PEGmoieties.

Plants that have been modified by breeding, mutagenesis or geneticengineering, e. g. have been rendered tolerant to applications ofspecific classes of herbicides, such as hydroxyphenylpyruvatedioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors,such as sulfonyl ureas (see e. g. U.S. Pat. No. 6,222,100, WO 01/82685,WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) orimidazolinones (see e. g. U.S. Pat. No. 6,222,100, WO 01/82685, WO00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073);enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such asglyphosate (see e. g. WO 92/00377); glutamine syn-thetase (GS)inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) oroxynil herbicides (see e. g. U.S. Pat. No. 5,559,024) as a result ofconventional methods of breeding or genetic engineering. Severalcultivated plants have been rendered tolerant to herbicides byconventional methods of breeding (mutagenesis), e. g. Clearfield® summerrape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.imazamox. Genetic engineering methods have been used to rendercultivated plants such as soybean, cotton, corn, beets and rape,tolerant to herbicides such as glyphosate and glufosinate, some of whichare commercially available under the trade names RoundupReady®(glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink®(glufosinate-tolerant, Bayer CropScience, Germany).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more insecticidal proteins,especially those known from the bacterial genus Bacillus, particularlyfrom Bacillus thuringiensis, such as δ-endotoxins, e. g. CryIA(b),CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c;vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A;insecticidal proteins of bacteria colonizing nematodes, e. g.Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, suchas scorpion toxins, arachnid toxins, wasp toxins, or otherinsect-specific neurotoxins; toxins produced by fungi, suchStreptomy-cetes toxins, plant lectins, such as pea or barley lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be understood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, e. g. WO 02/015701). Further examples of such toxins orgenetically modified plants capable of synthesizing such toxins aredisclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451 878, WO 03/18810 and WO 03/52073. The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e. g. in the publicationsmentioned above. These insecticidal proteins contained in thegenetically modified plants impart to the plants producing theseproteins tolerance to harmful pests from all taxonomic groups ofathropods, especially to beetles (Coeloptera), two-winged insects(Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).Genetically modified plants capable to synthesize one or moreinsecticidal proteins are, e. g., described in the publicationsmentioned above, and some of which are commercially available such asYieldGard® (corn cultivars producing the Cry1Ab toxin), YieldGard® Plus(corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corncultivars producing the Cry9c toxin), Herculex® RW (corn cultivarsproducing Cry34Ab1, Cry35Ab1 and the enzymePhosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cottoncultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivarsproducing the Cry1Ac toxin), Bollgard® II (cotton cultivars producingCry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing aVIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin);Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g.Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivarsproducing the Cry1Ab toxin and PAT enyzme), MIR604 from Syngenta SeedsSAS, France (corn cultivars producing a modified version of the Cry3Atoxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium(corn cultivars producing the Cry3Bb1 toxin), IPC 531 from MonsantoEurope S.A., Belgium (cotton cultivars producing a modified version ofthe Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium(corn cultivars producing the Cry1F toxin and PAT enzyme).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe resistance or tolerance of those plants to bacterial, viral orfungal pathogens. Examples of such proteins are the so-called“pathogenesis-related proteins” (PR proteins, see, e. g. EP-A 392 225),plant disease resistance genes (e. g. potato cultivars, which expressresistance genes acting against Phytophthora infestans derived from themexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potatocultivars capable of synthesizing these proteins with increasedresistance against bacteria such as Erwinia amylvora). The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e. g. in the publicationsmentioned above.

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe productivity (e. g. bio mass production, grain yield, starchcontent, oil content or protein content), tolerance to drought, salinityor other growth-limiting environmental factors or tolerance to pests andfungal, bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve human or animalnutrition, e. g. oil crops that produce health-promoting long-chainomega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera®rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve raw materialproduction, e. g. potatoes that produce increased amounts of amylopectin(e. g. Amflora® potato, BASF SE, Germany).

The compounds I and compositions thereof, respectively, are particularlysuitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida)and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leafspot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A.tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A.alternata), tomatoes (e. g. A. solani or A. alternata) and wheat;Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. oncereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A.hordei on barley; Bipolaris and Drechslera spp. (teleomorph:Cochliobolus spp.) on corn (e. g. D. maydis), cereals (e. g. B.sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria(formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheator barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: greymold) on fruits and berries (e. g. strawberries), vegetables (e. g.lettuce, carrots, celery and cabbages), rape, flowers, vines, forestryplants and wheat; Bremia lactucae (downy mildew) on lettuce;Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved treesand evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercosporaspp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C.beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina orC. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum:leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat;Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph:Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum),cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C.miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph:Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e.g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: blackdot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatumor C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight)on rice; Corynespora cassiicola (leaf spots) on soybeans andornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees;Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline,teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C.liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) andornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root andstem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (dampingoff) on soybeans; Drechslera (syn. Helminthosporium, teleomorph:Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, netblotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf;Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn.Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora(earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilumand/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri),soft fruits (E. veneta: anthracnose) and vines (E. ampelina:anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (blackmold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E.betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E.cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata(Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertellablepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn.Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium(teleomorph: Gibberella) spp. (wilt, root or stem rot) on variousplants, such as F. graminearum or F. culmorum (root rot, scab or headblight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F.solani on soybeans and F. verticillioides on corn; Gaeumannomycesgraminis (take-all) on cereals (e. g. wheat or barley) and corn;Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi:Bakanae disease); Glomerella cingulata on vines, pome fruits and otherplants and G. gossypii on cotton; Grainstaining complex on rice;Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. onrosaceous plants and junipers, e. g. G. sabinae (rust) on pears;Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) oncorn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leafrust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) onvines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) onsoybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snowmold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powderymildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M.fructigena (bloom and twig blight, brown rot) on stone fruits and otherrosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruitsand ground nuts, such as e. g. M. graminicola (anamorph: Septoriatritici, Septoria blotch) on wheat or M. fijiensis (black Sigatokadisease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g.P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor),tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsorapachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp.e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans(e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rapeand cabbage and P. betae (root rot, leaf spot and damping-off) on sugarbeets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can andleaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph:Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn;Phytophthora spp. (wilt, root, leaf, fruit and stem root) on variousplants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P.infestans: late blight) and broad-leaved trees (e. g. P. ramorum: suddenoak death); Plasmodiophora brassicae (club root) on cabbage, rape,radish and other plants; Plasmopara spp., e. g. P. viticola (grapevinedowny mildew) on vines and P. halstedii on sunflowers; Podosphaera spp.(powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g.P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such asbarley and wheat (P. graminis) and sugar beets (P. betae) and therebytransmitted viral diseases; Pseudocercosporella herpotrichoides(eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat orbarley; Pseudoperonospora (downy mildew) on various plants, e. g. P.cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila(red fire disease or, rotbrenner′, anamorph: Phialophora) on vines;Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown orleaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarfrust), P. graminis (stem or black rust) or P. recondita (brown or leafrust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e.g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis(tan spot) on wheat or P. teres (net blotch) on barley; Pyriculariaspp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) onrice and P. grisea on turf and cereals; Pythium spp. (damping-off) onturf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugarbeets, vegetables and various other plants (e. g. P. ultimum or P.aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leafspots, Physiological leaf spots) on barley and R. beticola on sugarbeets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape,potatoes, sugar beets, vegetables and various other plants, e. g. R.solani (root and stem rot) on soybeans, R. solani (sheath blight) onrice or R. cerealis (Rhizoctonia spring blight) on wheat or barley;Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots,cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley,rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) onrice; Sclerotinia spp. (stem rot or white mold) on vegetables and fieldcrops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e.g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) onwheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) oncereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph:Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g.S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelothecaspp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum and sugarcane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongosporasubterranea (powdery scab) on potatoes and thereby transmitted viraldiseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonosporablotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) onwheat; Synchytrium endobioticum on potatoes (potato wart disease);Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T.pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) ontobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola(syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) oncereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T.controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) onbarley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye;Uromyces spp. (rust) on vegetables, such as beans (e. g. U.appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae);Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae),corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab)on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt)on various plants, such as fruits and ornamentals, vines, soft fruits,vegetables and field crops, e. g. V. dahliae on strawberries, rape,potatoes and tomatoes.

The compounds I and compositions thereof, respectively, are alsosuitable for controlling harmful fungi in the protection of materials(e. g. wood, paper, paint dispersions, fiber or fabrics) and in theprotection of stored products. As to the protection of wood andconstruction materials, the particular attention is paid to thefollowing harmful fungi: Ascomycetes such as Ophiostoma spp.,Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomiumspp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes suchas Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp.,Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicilliumspp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetessuch as Mucor spp., and in addition in the protection of stored productsthe following yeast fungi are worthy of note: Candida spp. andSaccharomyces cerevisae.

Application of the inventive combinations to useful plants may also leadto an increase in the crop yield.

The compounds of formula I can be present in different crystalmodifications whose biological activity may differ. They are likewisesubject matter of the present invention.

The compounds I are employed as such or in form of compositions bytreating the fungi or the plants, plant propagation materials, such asseeds, soil, surfaces, materials or rooms to be protected from fungalattack with a fungicidally effective amount of the active substances.The application can be carried out both before and after the infectionof the plants, plant propagation materials, such as seeds, soil,surfaces, materials or rooms by the fungi.

Plant propagation materials may be treated with a composition comprisingat least one compound I prophylactically either at or before planting ortransplanting.

The invention also relates to agrochemical compositions comprising asolvent or solid carrier and at least one compound I and to the use forcontrolling harmful fungi.

An agrochemical composition comprises a fungicidally effective amount ofa compound I. The term “effective amount” denotes an amount of thecomposition or of the compounds I, which is sufficient for controllingharmful fungi on cultivated plants or in the protection of materials andwhich does not result in a substantial damage to the treated plants.Such an amount can vary in a broad range and is dependent on variousfactors, such as the fungal species to be controlled, the treatedcultivated plant or material, the climatic conditions and the specificcompound I used.

Compounds I, II and optionally III can be converted into customary typesof agrochemical compositions, e. g. solutions, emulsions, suspensions,dusts, powders, pastes and granules. The composition type depends on theparticular intended purpose; in each case, it should ensure a fine anduniform distribution of the compound according to the invention.

Examples for composition types are suspensions (SC, OD, FS), pastes,pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) orgranules (GR, FG, GG, MG), which can be water-soluble or wettable, aswell as gel formulations for the treatment of plant propagationmaterials such as seeds (GF).

Usually the composition types (e. g. SC, OD, FS, WG, SG, WP, SP, SS, WS,GF) are employed diluted. Composition types such as DP, DS, GR, FG, GGand MG are usually used undiluted.

The compositions are prepared in a known manner (cf. U.S. Pat. No.3,060,084, EP-A 707 445 (for liquid concentrates), Browning:“Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S.8-57 and ff. WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat.No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No.3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, NewYork, 1961), Hance et al.: Weed Control Handbook (8th Ed., BlackwellScientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulationtechnology (Wiley VCH Verlag, Weinheim, 2001).

The agrochemical compositions may also comprise auxiliaries which arecustomary in agrochemical compositions. The auxiliaries used depend onthe particular application form and active substance, respectively.

Examples for suitable auxiliaries are solvents, solid carriers,dispersants or emulsifiers (such as further solubilizers, protectivecolloids, surfactants and adhesion agents), organic and anorganicthickeners, bactericides, anti-freezing agents, anti-foaming agents, ifappropriate colorants and tackifiers or binders (e. g. for seedtreatment formulations).

Suitable solvents are water, organic solvents such as mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene,paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, alcohols such as methanol, ethanol, propanol, butanol andcyclohexanol, glycols, ketones such as cyclohexanone andgamma-butyrolactone, fatty acid dimethylamides, fatty acids and fattyacid esters and strongly polar solvents, e. g. amines such asN-methylpyrrolidone.

Solid carriers are mineral earths such as silicates, silica gels, talc,kaolins, limestone, lime, chalk, bole, loess, clays, dolomite,diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide,ground synthetic materials, fertilizers, such as, e. g., ammoniumsulfate, ammonium phosphate, ammonium nitrate, ureas, and products ofvegetable origin, such as cereal meal, tree bark meal, wood meal andnutshell meal, cellulose powders and other solid carriers.

Suitable surfactants (adjuvants, wtters, tackifiers, dispersants oremulsifiers) are alkali metal, alkaline earth metal and ammonium saltsof aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse®types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid(Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid(Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates,alkyl-arylsulfonates, alkyl sulfates, laurylether sulfates, fattyalcohol sulfates, and sulfated hexa-, hepta- and octadecanolates,sulfated fatty alcohol glycol ethers, furthermore condensates ofnaphthalene or of naphthalenesulfonic acid with phenol and formaldehyde,polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol,octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenylpolyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyetheralcohols, alcohol and fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignin-sulfite waste liquors and proteins, denatured proteins,polysaccharides (e. g. methylcellulose), hydrophobically modifiedstarches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland),polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates,polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidoneand the copolymers thereof.

Examples for thickeners (i. e. compounds that impart a modifiedflowability to compositions, i. e. high viscosity under staticconditions and low viscosity during agitation) are polysaccharides andorganic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco,U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt,U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).

Bactericides may be added for preservation and stabilization of thecomposition. Examples for suitable bactericides are those based ondichlorophene and benzylalcohol hemi formal (Proxel® from ICI orActicide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) andisothiazolinone derivatives such as alkylisothiazolinones andbenzisothiazolinones (Acticide® MBS from Thor Chemie).

Examples for suitable anti-freezing agents are ethylene glycol,propylene glycol, urea and glycerin.

Examples for anti-foaming agents are silicone emulsions (such as e. g.Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chainalcohols, fatty acids, salts of fatty acids, fluoroorganic compounds andmixtures thereof.

Suitable colorants are pigments of low water solubility andwater-soluble dyes. Examples to be mentioned and the designationsrhodamin B, C. I. pigment red 112, C. I. solvent red 1, pigment blue15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigmentblue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigmentred 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigmentorange 43, pigment orange 34, pigment orange 5, pigment green 36,pigment green 7, pigment white 6, pigment brown 25, basic violet 10,basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9,acid yellow 23, basic red 10, basic red 108.

Examples for tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®,Shin-Etsu, Japan).

Powders, materials for spreading and dusts can be prepared by mixing orconco-mitantly grinding the compounds I and, if appropriate, furtheractive substances, with at least one solid carrier.

Granules, e. g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active substances to solidcarriers. Examples of solid carriers are mineral earths such as silicagels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground synthetic materials, fertilizers, suchas, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate,ureas, and products of vegetable origin, such as cereal meal, tree barkmeal, wood meal and nutshell meal, cellulose powders and other solidcarriers.

Examples for composition types are:

1. Composition types for dilution with wateri) Water-soluble concentrates (SL, LS)

10 parts by weight of the active compound(s) according to the inventionare dissolved in 90 parts by weight of water or in a water-solublesolvent. As an alternative, wetting agents or other auxiliaries areadded. The active substance dissolves upon dilution with water. In thisway, a composition having a content of 10% by weight of active substanceis obtained.

ii) Dispersible concentrates (DC)

20 parts by weight of the active compound(s) according to the inventionare dissolved in 70 parts by weight of cyclohexanone with addition of 10parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilutionwith water gives a dispersion. The active substance content is 20% byweight.

iii) Emulsifiable concentrates (EC)

15 parts by weight of the active compound(s) according to the inventionare dissolved in 75 parts by weight of xylene with addition of calciumdodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 partsby weight). Dilution with water gives an emulsion. The composition hasan active substance content of 15% by weight.

iv) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) according to the inventionare dissolved in 35 parts by weight of xylene with addition of calciumdodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 partsby weight). This mixture is introduced into 30 parts by weight of waterby means of an emulsifying machine (Ultraturrax) and made into ahomogeneous emulsion. Dilution with water gives an emulsion. Thecomposition has an active substance content of 25% by weight.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s)according to the invention are comminuted with addition of 10 parts byweight of dispersants and wetting agents and 70 parts by weight of wateror an organic solvent to give a fine active substance suspension.Dilution with water gives a stable suspension of the active substance.The active substance content in the composition is 20% by weight.

vi) Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of the active compound(s) according to the inventionare ground finely with addition of 50 parts by weight of dispersants andwetting agents and prepared as water-dispersible or water-solublegranules by means of technical appliances (e. g. extrusion, spray tower,fluidized bed). Dilution with water gives a stable dispersion orsolution of the active substance. The composition has an activesubstance content of 50% by weight.

vii) Water-dispersible powders and water-soluble powders (WP, SP, SS,WS)

75 parts by weight of the active compound(s) according to the inventionare ground in a rotor-stator mill with addition of 25 parts by weight ofdispersants, wetting agents and silica gel. Dilution with water gives astable dispersion or solution of the active substance. The activesubstance content of the composition is 75% by weight.

viii) Gel (GF)

In an agitated ball mill, 20 parts by weight of the active compound(s)according to the invention are comminuted with addition of 10 parts byweight of dispersants, 1 part by weight of a gelling agent wetters and70 parts by weight of water or of an organic solvent to give a finesuspension of the active substance. Dilution with water gives a stablesuspension of the active substance, whereby a composition with 20% (w/w)of active substance is obtained.

2. Composition types to be applied undilutedix) Dustable powders (DP, DS)

5 parts by weight of the active compound(s) according to the inventionare ground finely and mixed intimately with 95 parts by weight of finelydivided kaolin. This gives a dustable composition having an activesubstance content of 5% by weight.

x) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active compound(s) according to the inventionis ground finely and associated with 99.5 parts by weight of carriers.Current methods are extrusion, spray-drying or the fluidized bed. Thisgives granules to be applied undiluted having an active substancecontent of 0.5% by weight.

xi) ULV solutions (UL)

10 parts by weight of the active compound(s) according to the inventionare dissolved in 90 parts by weight of an organic solvent, e. g. xylene.This gives a composition to be applied undiluted having an activesubstance content of 10% by weight.

The agrochemical compositions generally comprise between 0.01 and 95%,preferably between 0.1 and 90%, most preferably between 0.5 and 90%, byweight of active substance. The active substances are employed in apurity of from 90% to 100%, preferably from 95% to 100% (according toNMR spectrum).

Water-soluble concentrates (LS), flowable concentrates (FS), powders fordry treatment (DS), water-dispersible powders for slurry treatment (WS),water-soluble powders (SS), emulsions (ES) emulsifiable concentrates(EC) and gels (GF) are usually employed for the purposes of treatment ofplant propagation materials, particularly seeds. These compositions canbe applied to plant propagation materials, particularly seeds, dilutedor undiluted. The compositions in question give, after two-to-tenfolddilution, active substance concentrations of from 0.01 to 60% by weight,preferably from 0.1 to 40% by weight, in the ready-to-use preparations.Application can be carried out before sowing. Methods for applying ortreating agrochemical compounds and compositions thereof, respectively,on to plant propagation material, especially seeds, are known in theart, and include dressing, coating, pelleting, dusting and soakingapplication methods of the propagation material. In a preferredembodiment, the compounds or the compositions thereof, respectively, areapplied on to the plant propagation material by a method such thatgermination is not induced, e. g. by seed dressing, pelleting, coatingand dusting.

In a preferred embodiment, a suspension-type (FS) composition is usedfor seed treatment. Typcially, a FS composition may comprise 1-800 g/lof active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezingagent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1liter of a solvent, preferably water.

The active substances can be used as such or in the form of theircompositions, e. g. in the form of directly sprayable solutions,powders, suspensions, dispersions, emulsions, oil dispersions, pastes,dustable products, materials for spreading, or granules, by means ofspraying, atomizing, dusting, spreading, brushing, immersing or pouring.The application forms depend entirely on the intended purposes; it isintended to ensure in each case the finest possible distribution of theactive substances according to the invention.

Aqueous application forms can be prepared from emulsion concentrates,pastes or wettable powders (sprayable powders, oil dispersions) byadding water. To prepare emulsions, pastes or oil dispersions, thesubstances, as such or dissolved in an oil or solvent, can behomogenized in water by means of a wetter, tackifier, dispersant oremulsifier. Alternatively, it is possible to prepare concentratescomposed of active substance, wetter, tackifier, dispersant oremulsifier and, if appropriate, solvent or oil, and such concentratesare suitable for dilution with water.

The active substance concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.001 to 1% by weight of activesubstance.

The active substances may also be used successfully in theultra-low-volume process (ULV), it being possible to apply compositionscomprising over 95% by weight of active substance, or even to apply theactive substance without additives.

When employed in plant protection, the amounts applied are, depending onthe kind of effect desired, between 0.01 and 2.0 kg of active substanceper ha.

In treatment of plant propagation materials such as seeds, e. g. bydusting, coating or drenching seed, amounts of active substance of from1 to 1000 g, preferably from 5 to 100 g, per 100 kilogram of seed aregenerally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, ofactive substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, herbicides, bactericides,other fungicides and/or pesticides may be added to the active substancesor the compositions comprising them, if appropriate not untilimmediately prior to use (tank mix). These agents can be admixed withthe compositions according to the invention in a weight ratio of 1:100to 100:1, preferably 1:10 to 10:1.

Adjuvants which can be used are in particular organic modifiedpolysiloxanes such as Break Thru S 240®; alcohol alkoxylates such asAtplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®;EO/PO block polymers, e. g. Pluronic RPE 2035® and Genapol B®; alcoholethoxylates such as Lutensol XP 80®; and dioctyl sulfosucci-nate sodiumsuch as Leophen RA®.

The compositions according to the invention can, in the use form asfungicides, also be present together with other active substances, e. g.with herbicides, insecticides, growth regulators, fungicides or elsewith fertilizers, as pre-mix or, if appropriate, not until immediatelyprior to use (tank mix).

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; they are intended to ensure in each case the finestpossible distribution of the active compounds according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetting agent, tackifier, dispersant or emulsifier. However, it isalso possible to prepare concentrates composed of active substance,wetting agent, tackifier, dispersant or emulsifier and, if appropriate,solvent or oil, and such concentrates are suitable for dilution withwater.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active compound, or even to apply theactive compound without additives.

Oils of various types, wetting agents or adjuvants may be added to theactive compounds, even, if appropriate, not until immediately prior touse (tank mix). These agents are typically admixed with the compositionsaccording to the invention in a weight ratio of from 1:100 to 100:1,preferably from 1:10 to 10:1.

Suitable adjuvants in this sense are in particular: organically modifiedpolysiloxanes, for example Break Thru S 240®; alcohol alkoxylates, forexample Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON30®; EO/PO block polymers, for example Pluronic RPE 2035® and GenapolB®; alcohol ethoxylates, for example Lutensol XP 80®; and sodiumdioctylsulfosuccinate, for example Leophen RA®.

The compounds I and II or the mixtures or the corresponding formulationsare applied by treating the harmful fungi, the plants, seeds, soils,areas, materials or spaces to be kept free from them with a fungicidallyeffective amount of the mixture or, in the case of separate application,of the compounds I and II. Application can be before or after theinfection by harmful fungi.

The fungicidal action of the individual compounds and of thesynergistically active mixtures according to the invention wasdemonstrated by the tests below.

A) Microtiter Tests

The active compounds were formulated separately as a stock solutionhaving a concentration of 10000 ppm in dimethyl sulfoxide. The productsdimethoate, deltamethrin, lambda-cyalothrin, abamectin, hydromethylnon,fenbutadin-oxyd and indoxacarb were used as commercial finishedformulations and diluted with water to the stated concentration of theactive compound. The measured parameters were compared to the growth ofthe active compound-free control variant (100%) and the fungus-free andactive compound-free blank value to determine the relative growth in %of the pathogens in the respective active compounds.

These percentages were converted into efficacies.

An efficacy of 0 means that the growth level of the pathogenscorresponds to that of the untreated control; an efficacy of 100 meansthat the pathogens were not growing.

The expected efficacies of active compound mixtures were determinedusing Colby's formula (Colby, S.R. “Calculating synergistic andantagonistic responses of herbicide combinations”, Weeds, 15, pp. 20-22,1967) and compared with the observed efficacies.

E=x+y−x·y/100  Colby's formula:

-   E expected efficacy, expressed in % of the untreated control, when    using the mixture of the active compounds A and B at the    concentrations a and b-   x efficacy, expressed in % of the untreated control, when using the    active compound A at the concentration a-   y efficacy, expressed in % of the untreated control, when using the    active compound B at the concentration b

USE EXAMPLE 1

Activity against the late blight pathogen Phytophthora infestans Thestock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations. Azoospore suspension of Phytophthora infestans in an aqueous pea juicesolution was then added. The plates were placed in a watervapor-saturated chamber at temperatures of 18° C. Using an absorptionphotometer, the MTPs were measured at 405 nm on day 7 after theinoculation. The measured parameters were compared to the growth of theactive substance-free control variant (=100%) and the fungus- and activesubstance-free blank value to determine the relative growth in % of thepathogens in the individual active substances.

USE EXAMPLE 2

Activity against the rice blast pathogen caused by Pyricularia oryzaeThe stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Pyricularia oryzae in an aqueousbiomalt solution was then added. The plates were placed in a watervapor-saturated chamber at temperatures of 18° C. Using an absorptionphotometer, the microtiter plates were measured at 405 nm on day 7 afterthe inoculation. The measured parameters were compared to the growth ofthe active substance-free control variant (=100%) and the fungus- andactive substance-free blank value to determine the relative growth in %of the pathogens in the individual active substances.

TABLE 10 Calculated Active compounds/ efficacy ac- active compoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Ia = N-(3′,4′,5′- 0.004 — 3 — trifluorobiphenyl-2- yl)-3-difluoromethyl-1-methyl-1H- pyrazole-4- carboxamide Bixafen 0.25 — 6 — 0.063 — 6 —Isopyrazam 0.016 — 15 — Penflufen 0.25 — 5 — Sedaxane (trans 0.016 — 1 —diastereoisomer) Indoxacarb 1 — 0 — alpha-Cypermethrin 63 — 41 —Endosulfan 63 — 73 — 16 — 22 — Chlorfenapyr 63 — 38 — 4 — 17 —Flubendiamid 63 — 15 — 4 — 0 — Deltamethrin 4 — 0 — Hydramethylnon 4 — 5— Fenbutadin-oxyd 4 — 39 — Ia + Indoxacarb 0.004 + 1 1:250 35  3Bixafen +  0.25 + 63 1:250 63 44 alpha-Cypermethrin Bixafen +  0.063 +16 1:250 82 26 Endosulfan Bixafen +  0.25 + 63 1:250 87 42 ChlorfenapyrBixafen +  0.25 + 63 1:250 100 20 Flubendiamid Isopyrazam + 0.016 + 41:250 64 15 Deltamethrin Isopyrazam + 0.016 + 4 1:250 43 19Hydramethylon Isopyrazam + 0.016 + 4 1:250 83 30 ChlorfenapyrIsopyrazam + 0.016 + 4 1:250 48 15 Flubendiamid Penflufen +  0.25 + 631:250 100 74 Endosulfan Sedaxane (trans 0.016 + 4 1:250 65 40stereoisomer) + Fenbutadin-oxyd

USE EXAMPLE 3

Activity against leaf blotch on wheat caused by Septoria tritici Thestock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP) and diluted with water to the stated concentrations. Aspore suspension of Septoria tritici in an aqueous biomalt solution wasthen added. The plates were placed in a water vapor-saturated chamber attemperatures of 18° C. Using an absorption photometer, the microtiterplates were measured at 405 nm on day 7 after the inoculation. Themeasured parameters were compared to the growth of the activesubstance-free control variant (=100%) and the fungus- and activesubstance-free blank value to determine the relative growth in % of thepathogens in the individual active substances.

TABLE 11 Calculated Active compounds/ efficacy ac- active compoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Ia 0.016 — 29 — Bixafen 0.063 — 48 — Isopyrazam 0.063 — 58 — Penflufen0.25 — 44 — Sedaxane (trans 0.25 — 57 — diastereoisomer) Acephate 4 — 2— Dimethoate 4 — 2 — Methamidophos 4 — 5 — Deltamethrin 63 — 3 — 16 — 0— Endosulfan 63 — 26 — 16 — 3 — Hydramethylnon 63 — 4 — 16 — 0 —Chlorfenapyr 16 — 8 — Indoxacarb 63 — 19 — 16 — 9 — Terbufos 16 — 14 —Aldicarb 16 — 7 — lambda-Cyalothrin 63 — 29 — 16 — 10 — Flubendiamid 63— 37 — Ia + Acephate 0.016 + 4  1:250 73 30 Ia + Dimethoate 0.016 + 4 1:250 49 30 Ia + Methamidophos 0.016 + 4  1:250 68 32 Bixafen + 0.063 +16 1:250 95 48 Deltamethrin Bixafen + 0.063 + 16 1:250 96 49 EndosulfanBixafen + 0.063 + 16 1:250 71 48 Hydramethylnon Bixafen + 0.063 + 161:250 71 52 Chlorfenapyr Bixafen + 0.063 + 16 1:250 78 52 IndoxacarbIsopyrazam + 0.063 + 16 1:250 91 64 Terbufos Isopyrazam + 0.063 + 161:250 82 61 Aldicarb Isopyrazam + 0.063 + 16 1:250 80 58 DeltamethrinIsopyrazam + 0.063 + 16 1:250 85 62 lambda-Cyalothrin Isopyrazam +0.063 + 16 1:250 100 60 Endosulfan Isopyrazam + 0.063 + 16 1:250 89 58Hydramethylnon Isopyrazam +  0.63 + 16 1:250 83 62 ChlorfenapyrIsopyrazam + 0.063 + 16 1:250 83 62 Indoxacarb Penflufen +  0.25 + 631:250 100 46 Deltamethrin Penflufen +  0.25 + 63 1:250 97 58 EndosulfanPenflufen +  0.25 + 63 1:250 76 46 Hydramethylnon Penflufen +  0.25 + 631:250 75 54 Indoxacarb Sedaxane +  0.25 + 63 1:250 90 59 DeltamethrinSedaxane +  0.25 + 63 1:250 89 67 lambda-Cyalothrin Sedaxane +  0.25 +63 1:250 100 68 Endosulfan Sedaxane +  0.25 + 63 1:250 100 73Flubendiamid

USE EXAMPLE 4 Activity Against Alternaria solani

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Alternaria solani in an aqueousbiomalt solution was then added. The plates were placed in a watervapor-saturated chamber at a temperature of 18° C. Using an absorptionphotometer, the MTPs were measured at 405 nm 7 days after theinoculation.

TABLE 12 Calculated Active compounds/ efficacy ac- active compoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Ia 0.004 — 29 — Bixafen 0.004 — 0 — Isopyrazam 0.016 — 2 — Penflufen0.063 — 0 — Sedaxane (trans 0.25 — 20 — diastereoisomer) 0.063 — 0 —Acephate 1 — 3 — Methamidophos 63 — 0 — 1 — 8 — Deltamethrin 16 — 0 — 4— 5 — 1 — 0 — Abamectin 1 — 2 — Hydramethylnon 1 — 7 — Endosulfan 16 —13 — Bifenthrin 63 — 1 — alpha-Cypermethrin 63 — 0 — Flubendiamid 63 — 0— Indoxacarb 16 — 0 — Ia + Acephate 0.004 + 1  1:250 72 31 Ia +Methamidophos 0.004 + 1  1:250 78 35 Bixafen + 0.004 + 11 1:250 29 0Deltamethrin Bixafen + 0.004 + 1  1:250 28 2 Abamectin Bixafen + 0.004 +1  1:250 31 7 Hydramethylnon Isopyrazam + 0.016 + 4  1:250 28 6Deltamethrin Penflufen + 0.063 + 16 1:250 24 0 Deltamethrin Penflufen +0.063 + 16 1:250 34 13 Endosulfan Sedaxane +  0.25 + 63 1:250 48 20Methamidophos Sedaxane +  0.25 + 63 1:250 39 20 Bifenthrin Sedaxane + 0.25 + 63 1:250 48 20 alpha-Cypermethrin Sedaxane + 0.063 + 16 1:250 3413 Endosulfan Sedaxane +  0.25 + 63 1:250 100 20 Flubendiamid Sedaxane +0.063 + 16 1:250 21 0 Indoxacarb

USE EXAMPLE 5 Activity Against Colletotrichum truncatum

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Colletotrichum truncatum in anaqueous biomalt solution was then added. The plates were placed in awater vapor-saturated chamber at a temperature of 18° C. Using anabsorption photometer, the MTPs were measured at 405 nm 7 days after theinoculation.

TABLE 13 Calculated Active compounds/ efficacy ac- active compoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Bixafen 0.25 — 6 — Isopyrazam 0.25 — 14 — Sedaxane (trans 0.25 — 3 —diastereoisomer) Endosulfan 63 — 8 — Flubendiamid 63 — 0 — Bixafen +0.25 + 63 1:250 37 14 Endosulfan Bixafen + 0.25 + 63 1:250 100 6Flubendiamid Isopyrazam + 0.25 + 63 1:250 43 21 Endosulfan Sedaxane +0.25 + 63 1:250 100 3 Flubendiamid

USE EXAMPLE 6 Activity Against Leptospharium Nodorum

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Leptosphaerium nodorum in anaqueous biomalt solution was then added. The plates were placed in awater vapor-saturated chamber at a temperature of 18° C. Using anabsorption photometer, the MTPs were measured at 405 nm 7 days after theinoculation.

TABLE 14 Calculated Active compounds/ efficacy ac- active coumpoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Bixafen 0.25 — 16 — Isopyrazam 0.25 — 13 — Sedaxane (trans 0.25 — 17 —diastereoisomer) Endosulfan 63 — 5 — Chlorfenapyr 63 — 8 — Flubendiamid63 — 22 — Bixafen + 0.25 + 63 1:250 58 20 Endosulfan Bixafen + 0.25 + 631:250 44 22 Chlorfenapyr Bixafen + 0.25 + 63 1:250 100 34 FlubendiamidIsopyrazam + 0.25 + 63 1:250 68 18 Endosulfan Sedaxane + 0.25 + 63 1:250100 35 Flubendiamid

USE EXAMPLE 7 Activity Against Fusarium culmorum

The stock solutions were mixed according to the ratio, pipetted onto amicro titer plate (MTP) and diluted with water to the statedconcentrations. A spore suspension of Fusarium culmorum in an aqueousbiomalt solution was then added. The plates were placed in a watervapor-saturated chamber at a temperature of 18° C. Using an absorptionphotometer, the MTPs were measured at 405 nm 7 days after theinoculation.

TABLE 15 Calculated Active compounds/ efficacy ac- active compoundConcentration Observed cording to mixture [ppm] Ratio efficacy Colby (%)Sedaxane (trans 0.25 — 2 — diastereoisomer) Flubendiamid 63 — 3 —Sedaxane + 0.25 + 63 1:250 100 5 Flubendiamid

B) Greenhouse Tests

The active substances were formulated separately or together as a stocksolution comprising 25 mg of active substance which was made up to 10 mlusing a mixture of ace-tone and/or dimethyl sulfoxide (DMSO) and theemulsifier Wettol EM 31 (wetting agent having emulsifying and dispersingaction based on ethoxylated alkylphenols) in a volume ratio ofsolvent/emulsifier of 99 to 1. This solution was then made up to 100 mlusing water. This stock solution was diluted with thesolvent/emulsifier/water mixture described to the active substanceconcentration given below.

USE EXAMPLE 8 Activity Against Early Blight on Tomatoes Caused byPhytophthora infestans with Protective Application

Young seedlings of tomato plants were grown in pots. The plants weresprayed to runoff with an aqueous suspension containing theconcentration of active substance stated below. The next day, thetreated plants were inoculated with an aqueous suspension of sporangiaof Phytophthora infestans. After inoculation, the trial plants wereimmediately transferred to a humid chamber. After 6 days at 18 to 20° C.and a relative humidity close to 100%, the extent of fungal attack onthe leaves was visually assessed as % diseased leaf area.

USE EXAMPLE 9 Curative Action Against Puccinia recondita on Wheat (BrownRust of Wheat)

Leaves of potted wheat seedlings of the cultivar “Kanzler” were dustedwith a suspension of spores of brown rust of wheat (Puccinia recondita).The plants were then placed in a chamber with high atmospheric humidity(90 to 95%), at 20-22° C., for 24 hours. During this time, the sporesgerminated and the germinal tubes penetrated into the leaf tissue. Thenext day, the infected plants were sprayed to runoff point with anaqueous suspension having the concentration of active substance statedbelow. After drying of the sprayed suspension, the test plants werereturned into the greenhouse and cultivated at temperatures between 20and 22° C. and at 65 to 70% relative atmospheric humidity for a further7 days. The extent of the rust development on the leaves was thendetermined visually.

USE EXAMPLE 10 Protective Action Against Puccinia recondita on Wheat(Brown Rust of Wheat)

Leaves of potted wheat seedlings of the cultivar “Kanzler” were sprayedto runoff point with an aqueous suspension having the concentration ofactive substance stated below. The next day, the treated plants weredusted with a suspension of spores of brown rust of wheat (Pucciniarecondita). The plants were then placed in a chamber with highatmospheric humidity (90 to 95%), at 20-22° C., for 24 hours. Duringthis time, the spores germinated and the germinal tubes penetrated intothe leaf tissue. The next day, the test plants were returned into thegreenhouse and cultivated at temperatures between 20 and 22° C. and at65 to 70% relative atmospheric humidity for a further 7 days. The extentof the rust development on the leaves was then determined visually.

USE EXAMPLE 11 Protective Action Against Blumeria Graminis Tritici onWheat (Mildew of Wheat)

Leaves of potted wheat seedlings of the cultivar “Kanzler” were sprayedto runoff point with an aqueous suspension having the concentration ofactive substance stated below. The next day, the treated plants weredusted with a suspension of spores of mildew of wheat (Blumeria graministritici). The plants were then returned into the greenhouse andcultivated at temperatures between 20 and 24° C. and at 60 to 90%relative atmospheric humidity for a further 7 days. The extent of themildew development on the leaves was then determined visually.

USE EXAMPLE 12 Protective Action Against Sphaerotheca Fuliginea onCucumber (Mildew of Cucumber)

Leaves of potted cucumber seedlings (in the germ layer stage) weresprayed to runoff point with an aqueous suspension having theconcentration of active substance stated below. The next day, thetreated plants were dusted with a suspension of spores of mildew ofcucumber (Sphaerotheca fuliginea). The plants were then returned intothe greenhouse and cultivated at temperatures between 20 and 24° C. andat 60 to 80% relative atmospheric humidity for a further 7 days. Theextent of the mildew development on the seed leaves was then determinedvisually.

1. A mixture for controlling phytopathogenic harmful fungi comprising,as active components, 1) at least one 1-methylpyrazol-4-ylcarboxanilideof the formula I

in which the substituents are as defined below: R¹ is C₁-C₄-alkyl orC₁-C₄-haloalkyl; R² is hydrogen or halogen; X is hydrogen or fluorine; Qis a direct bond; R³ is phenyl substituted with two or three halogenatoms; and 2) at least one active compound II, selected from the activecompound groups A) to K): A) an organo(thio)phosphate selected from thegroup consisting of acephate, azamethiphos, azinphos-methyl,chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion,fenthion, isoxathion, malathion, methamidophos, methidathion,methyl-parathion, mevinphos, monocrotophos, oxy-demeton-methyl,paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon,phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos,tetrachlorvinphos, terbufos, triazophos and trichlorfon; B) a carbamateselected from the group consisting of: alanycarb, aldicarb, bendiocarb,benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb,furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur,thiodicarb and triazamate; D) a growth regulator selected from the groupconsisting of the following a) chitin synthesis inhibitors:benzoylureas: chlorfluazuron, cyramazin, -flucycloxuron, hexaflumuron,lufenuron, novaluron, triflumuron; buprofezin, diofenolan, hexythiazox,etoxazole and clofentazine; b) ecdysone antagonists: halofenozide,methoxyfenozide, tebufenozide, and azadirachtin; c) juvenoids:pyriproxyfen, methoprene and fenoxycarb; d) lipid biosynthesisinhibitors: spirodiclofen, spiromesifen and spirotetramat; E) a GABAantagonist compound selected from the group consisting of endosulfan,ethiprole, vaniliprole, pyrafluprole, pyriprole and the phenylpyrazoleof the formula E¹

F) a macrocyclic lactone insecticide selected from the group consistingof abamectin, emamectin, milbemectin, lepimectin, spinosad andspinetoram; G) a METI I acaricide selected from the group consisting offenazaquin, pyridaben, tebufenpyrad, tolfenpyrad and flufenerim H) aMETI II and III compound selected from the group consisting ofacequinocyl, fluacyprim and hydramethylnon; an oxidative phosphorylationinhibitor compound selected from the group consisting of cyhexatin,diafenthiuron, fenbutatin oxide and propargite; a compound selected fromthe group consisting of amidoflumet, benclothiaz, bifenazate,bistrifluron, cartap, chlorfenapyr, cryomazine, cyazypyr (HGW86),cyenopyrafen, cyflumetofen, flonicamid, flubendiamide, flupyrazofos,imicyafos, indoxacarb, metaflumizone, piperonyl butoxide, pymetrozine,pyridalyl, pyrifluquinazon, thiocyclam and the thiazole compound offormula K¹

in a synergistically effective amount.
 2. The fungicidal mixture ofclaim 1, comprising as component 1) a 1-methylpyrazol-4-ylcarboxanilideof the formula I where R¹ is C₁-C₄-haloalkyl, R² is hydrogen, Q is adirect bond and R³ is phenyl substituted by two or three halogen atoms.3.-4. (canceled)
 5. The fungicidal mixture of claim 1, comprising ascomponent 1) a 1-methylpyrazol-4-ylcarboxanilide of the formula I whereR¹ is C₁-C₄-alkyl, R² is halogen, X is hydrogen, Q is a direct bond, andR³ is C₁-C₆-alkyl.
 6. The fungicidal mixture of claim 1, comprising anadditional active compound.
 7. The fungicidal mixture of claim 1,comprising the components 1) and 2) in a weight ratio of from 100:1 to1:100.
 8. A composition, comprising at least one liquid or solid carrierand the mixture of claim
 1. 9. A method for controlling phytopathogenicharmful fungi, comprising treating the fungi, their habitat or plants tobe protected against fungal attack, the soil, seed, areas, materials orspaces with an effective amount of at least one component 1) and atleast one component 2) 1) a compound of formula I

in which the substituents are as defined below: R¹ is C₁-C₄-alkyl orC₁-C₄-haloalkyl; R² is hydrogen or halogen; X is hydrogen or fluorine; Qis a direct bond; R³ is phenyl substituted with two or three halogenatoms; and 2) a compound II, selected from the active compound groups A)to K): A) an organo(thio)phosphate selected from the group consisting ofacephate, azamethiphos, azinphos-methyl, chlorpyrifos,chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos,dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion,malathion, methamidophos, methidathion, methyl-parathion, mevinphos,monocrotophos, oxy-demeton-methyl, paraoxon, parathion, phenthoate,phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,triazophos and trichlorfon; B) a carbamate selected from the groupconsisting of: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl,carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl,oxamyl, pirimicarb, propoxur, thiodicarb and triazamate; D) a growthregulator selected from the group consisting of the following a) chitinsynthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin,-flucycloxuron, hexaflumuron, lufenuron, novaluron, triflumuron;buprofezin, diofenolan, hexythiazox, etoxazole and clofentazine; b)ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, andazadirachtin; c) juvenoids: pyriproxyfen, methoprene and fenoxycarb; d)lipid biosynthesis inhibitors: spirodiclofen, spiromesifen andspirotetramat; E) a GABA antagonist compound selected from the groupconsisting of endosulfan, ethiprole, vaniliprole, pyrafluprole,pyriprole and the phenylpyrazole of the formula E¹

F) a macrocyclic lactone insecticide selected from the group consistingof abamectin, emamectin, milbemectin, lepimectin, spinosad andspinetoram; G) a METI I acaricide selected from the group consisting offenazaquin, pyridaben, tebufenpyrad, tolfenpyrad and flufenerim H) aMETI II and III compound selected from the group consisting ofacequinocyl, fluacyprim and hydramethylnon; an oxidative phosphorylationinhibitor compound selected from the group consisting of cyhexatin,diafenthiuron, fenbutatin oxide and propargite; a compound selected fromthe group consisting of amidoflumet, benclothiaz, bifenazate,bistrifluron, cartap, chlorfenapyr, cryomazine, cyazypyr (HGW86),cyenopyrafen, cyflumetofen, flonicamid, flubendiamide, flupyrazofos,imicyafos, indoxacarb, metaflumizone, piperonyl butoxide, pymetrozine,pyridalyl, pyrifluquinazon, thiocyclam and the thiazole compound offormula K¹

in a synergistically effective amount.
 10. The method according to claim9, wherein the components 1) and 2) are applied simultaneously asindividual components or as a mixture, separately, or in succession. 11.The method according to claim 10, wherein the components 1) and 2) areapplied in an amount of from 5 g/ha to 2000 g/ha.
 12. The methodaccording to claim 10, wherein the components 1) and 2) are applied inan amount of from 1 g to 1000 g per 100 kg of seed.
 13. The method ofclaim 9, wherein component 1) is a 1-methylpyrazol-4-ylcarboxanilide ofthe formula I where R¹ is C₁-C₄-haloalkyl, R² is hydrogen, Q is a directbond and R³ is phenyl substituted by two or three halogen atoms. 14.-15.(canceled)
 16. The method of claim 9, wherein component 1) is a1-methylpyrazol-4-ylcarboxanilide of the formula I where R¹ isC₁-C₄-alkyl, R² is halogen, X is hydrogen, Q is a direct bond, and R³ isC₁-C₆-alkyl.
 17. A seed, of treated with the mixture claim 1 in anamount of from 1 g to 1000 g per 100 kg of seed.
 18. The fungicidalmixture of claim 1, wherein the active compound II is a macrocycliclactone insecticide selected from the group consisting of abamectin,emamectin, milbemectin, lepimectin, spinosad and spinetoram.
 19. Themethod of claim 9, wherein the active compound II is a macrocycliclactone insecticide selected from the group consisting of abamectin,emamectin, milbemectin, lepimectin, spinosad and spinetoram.